Manufacture of sulphurized hydrocarbons



Mal'Cl'l 1, W, E, FORNEY 2,109,692

MANUFACTURE OF SULPHURIZED HYDROCARBONS Filed Feb. 1o, 195e POLYMER 2 OIL GAS REACTION CHAM BER A|R I' NVENTOR WH-LIAM E. FORNEY ii mi 2 PRODUCT ATTORNEY Patented Mar. l, 1938 UNITED STATES 2,109,692 MANUEAc'rUnE .or svunmuzsn mnocAanoNs William E. Forney, Merchantville, J., assignoi' to Power Patents Company, Hillside. N. J., a

corporation of Maine Application February 1o, 193s, semina. 63,071

13 Claims.

This invention relates to a. product of manufacture and process for manufacturingfextreme' pressure lubricants and cutting oil, and more particularly the invention relates to the production of extreme pressure lubricants and cutting oils containing combined sulphur.

The process of this invention is an improvement on known processes for the manufacture of extreme pressure lubricants or bases in which a polymer oil, such as that produced by the action of various polymerizing agents on cracked gasoline, is sulphurized by heating the polymer with cant. Ihese lubricants in turn are used extensively in the lubrication of hypoid gears and in factin any place where extreme bearing pres sures are developed.

'I'he primary object of the present invention is to provide an improved process` for manufacturing extreme pressure lubricants and more particularly an extreme pressure lubricant base containing combined sulphur. i

A further object of the invention is to provide a process for manufacturing a sulphurized base which is relatively light in color and relatively uid compared to previously known compositions of this general character. Another object of the invention is to provide process for manufacturing an extreme pressure lubricant base from polymerized aromatic hy-l drocarbons.

Accordingly the features of the present invention involvethe production of a polymerized hydrocarbon preferably containing very substantial proportions of polymerired aromatic constituents,

.' effecting a reaction between such a polymer and hydrogen sulphide to cause the combination of sulphur with the polymerized hydrocarbons to thereby produce a base product containing relatively large percentages of sulphur, which base has a relatively high degree of fluidity and is relatively light in color.

Other features and advantages of the process and product of the present invention will be apparent to those skilled in the art from the following detailed description thereof taken in con- (cL aso-1r) '1 nection with the accompanying drawing, in which:

The single figure is 1a flow diagram of an apparatus adapted to carry,v out theimproved mocess `for the production'of the improved extreme pressure lubricant bases' l The cracked gasolinenormally treated by sulphuric acidand otherv polymerizing agents such as phosphoric acid, aluminum chloride, zinc chloride, fullers earth fand adsorptive clays, rarely contains more than. a few per cent of aromatic hydrocarbons. These gasolines hcw- .ever contain considerable proportions of unsaturated olenic hydrocarbons which are polymerized when brought in contact with the treating agents mentioned above. The resulting polymers have been sulphurized by heating them t'o temperatures Aof from 375 to 450 F. in the presence of flowers of sulphur.

The polymer productv preferably employedin accordance with the features of the present invention comprises ahighly aromatic material produced by short time contact of a cracked gasoline containing from 50% to 85% of aromatic hydrocarbons with one of the polymerizing agents referred to above, preferably phosphoric acid. Gasolinesof this character are described for example in the patent to Forward No'. 2.007.081. granted July 2nd, 1935. 'I'hese high aromatic gasolines produced by the process of ,this Forward patent are largely comprised of side `chain aromatic hydrocarbons such as the alkylated benzenes. Some of the -side chains on these -aromatic hydrocarbons apparently contain unsaturated linkages so that the contact of the gasoline with the polymerizing agent causes the formation of aromatic polymers. ,'Iherefore, 'while any gasoline polymer may be used in the process of the present invention, the highly aromatic polymer is preferred.A In general the polymers made by using phosphoric acid have high specific lgravities approaching that ofwater, viscosities of from to 500 sec. (Saybolt) at 100- F., low viscosity indices, pour points-of from 0 to 30 F. andV low (2 to 3.) added bromine values but high (68 to '10) bromine substitution values.

Referring to the figure of the drawing, the polymer .oil to be used in the process is withdrawn from a supply tank 2 and passed through a valve-controlled line I into a scrubbing tower 6, in which the oil is brought in contact with certain more or less waste gases resulting from subsequent steps in the operation, and containing hydrogen sulphide. In the scrubber 6 the polymer oil passes downwardly over the 4bubble cap Cit drogen sulphide contained in the gas. 'I'he waste gases of the process including considerable steam or water are discharged tltough a valved iine l. The temperature maintained in the tap oi the icru'b'ber will be substantially that of the polymer oil introduced, which should be in the neighborhood of about 100 to 125 F. The temperature at the bottom of the scrubber 6 will be somewhat higherbecause of the higher temperature o! the gases introduced into the bottom of the scrubber.

'Ihe polymer oil reaching the bottom of the scrubberbl and containing some absorbed or reacted hydrogen sulphide is withdrawn through a valve-controlled line Il and introduced into an ejector mixing nozzle I2 in which the polymer oil is thoroughly atomized and mixed with hydrogen sulphide gas and oxygen or air. The hydrogen sulphide gas for this purpose is introduced into the mixer I2 through a valved line I4 while the oxygen or air is introduced through a valved line I6. The resulting mixture of polymer oil, hydrogen sulphide and oxygen is passed in a stream through a tubular heating coil IB mounted in a heater 20, and the resulting mixture is raised to a temperature of about 250 F. (by the external heating and the heat of reaction). and then conducted through a transfer line 22 and distributor 24 into a body of oil maintained in a time reaction chamber 26.

While the exact mechanism of the reaction proceeding in the coil Il and chamber 26 is not definitely known, it may be explained by the following equations in which nascent sulphur is formed from the hydrogen sulphide and reacted with the hydrocarbons of the polymer oil:

In the last equation R represents any hydrocarbon or polymerized hydrocarbon molecule, and it is to be understood that one or more sulphur atoms may be combined with a single molecule of the polymer oil. The body of oil maintained in the reaction chamber 26 may bear any desired relation to the amount of oil introduced into the chamber in any given time thereby securing the desired time reaction. The chamber 26 is preferably insulated in order to prevent heat loss so that the body of oil is maintained at a practically constant temperature while it is being continuously agitated and contacted with unreacted hydrogen sulphide and oxygen discharged from the coil Il. A substantial proportion of the reaction may be eiected' in the coil I8 although an extremely long coil is not necessary. The mixture of gases separating from the body of oil in chamber 2l, including the water vapor formed, are withdrawn through a vapor line 26 and introduced into the lower part of the scrubber 6.

The reaction product formed in coil i6 and chamber 26 and containing from 8% to approximately 20% oi' combined sulphur may be withdrawn and used as such in the manufacture of extreme pressure lubricants. This material has a brown color and is readily handled at ordinary temperatures for blending with petroleum oil lubricant stock to make the desired final product. A light colored extreme pressure lubricant having a relatively low viscosity is produced suitable for4 eiIectively lubricating various types of bearings at relatively low temperatures. As an example of the eiiectiveness of this base, a bright trays and codinctsthe cases raising upwardly therethrough and absorbs or reacts with the hyl stock blend containing 10% of the base showed a 30% increase in load carrying capacity.

Where it is desirable to put larger proportions of sulphur into the sulphur base product, the material produced in the reaction chamber 26 is withdrawn through an ejector nozzle 30 in which it is mixed with additional quantities of oxygen or air'and hydrogen sulphide introduced through valved lines 32 and 34. An intimate mixture of the partially sulphurized product withdrawn from chamber 26 and the gases, is passed through a heating coil 36 mounted in a heater 38. In' this heating coilthe mixture is raised to a temperature of approximately 275 F. so that a f urther reaction is obtained to produce a product containing increasing percentages of sulphur. The mixture in the coil 36 is passed through a transfer line 40 and distributor 42 into a body of the sulphurized polymer oil maintained in a second enlarged reaction chamber 44. 'I'he partially sulphurized polymer is intimately contacted and agitated with the gases in the chamber 44 until the desired amount of sulphur is combined. 'I'he waste gases are discharged through a line 46 and passed with the gases in line 28 into the lower part of scrubber 6.,-

While the temperature in the chamber 44 may be suitably maintained by insulating the chamber, the reaction may be aided materially, by withdrawing -a, portion of the partially reacted polymer oil from chamber 44 and conducting it through a valved line 48, a pump 50 and a line 52, into the stream of gases and oil mixture going to the heating coil 36. In passing the partially reacted polymer into this stream of gas and oil, it is again brought in contact and heatedl in the presence of hydrogen sulphide and oxygen or in the presence of nascent sulphur. 'I'hese conditions are favorable for e'ecting. the desired combination f the sulphur with the polymer oil at as low a temperature as possible, so that the desirable characteristics of the product are not destroyed. In many instances, it is desirable to produce a lubricant `having a relatively low viscosity and relatively light color for the lubrication of bearings in automobiles and aircraft which are operated at relatively low temperatures. The extreme pressure lubricants previously produced are very gummy, viscous and black compositions which are diiiicult to use except for the lubrication of transmission gears and similar types of equipment.

The completely reacted product is withdrawn from the reaction chamber 44 through a valved line 54 into a nishing chamber 56 in which the product is stripped of any occluded hydrogen sulphide and other sulphur containing gases. Gas from a cracking unit which isfree of hydrogen sulphide or other inert gas is introduced into the chamber 56 through a valved line 58 and a distributor 60 to accomplish this purpose. The waste gases are discharged from the chamber 56 through a valved gas line 62 while the finished sulphurized base product is withdrawn through a valved line 64. 'I'he gas introduced into the body of the product in the finisher 56 strips out the occluded sulphur gases and substantially cools the material which may be blended directly with any desired lubricating stock or packed for shipment.

'I'he sulphurized products of the present invention when produced from the phosphoric acid polymers, do not have the odensive odor which is common with products made for example, from sulphuric acid polymers and flowers of sulphur. 'I'he use of hydrogen sulphide in the manner de- 'scribed appears to give dlileren't compounds iroml process of the present invention, that the appa,

ratus may be operated continuously or intermittently, but the process is continuous in the sense that the materials going into the manufacture of the product are continuously being acted upon to produce the desired sulphurized polymer base. Furthermore, it is to be understood that the ratio of hydrogen sulphide to oxygen introduced into the mixing nozzles l2 and 3l is controlled to give the proper proportions of these gases. Where air is used to supply the oxygen, some excess of air may be introduced so that the hydrogen sulphide will be completely reacted as far as possible.

- 'Ihe hydrogen sulphide gas used in the abovedescribed process may be obtained from any suitablesource. For example, refinery gases obtained in the distillation and cracking of petroleum oil may be employed where theyl contain a substantial proportion of hydrogen sulphide..

'Ihe hydrocarbon gases presentalong with the hydrogen sulphide will haveno adverse effects upon the reactions taking place. Hydrogen vsulphide may be obtained from other industrial sources -or may be generated by decomposition of sulphide ores, metallic sulphides or other sul-` Dhides.

From the above description of the preferred process and product of the present invention, it is apparent that various modifications may be made in the details of procedure without departing from the spirit and scope of the present invention.

Having thus described the invention in its pre'- ferred form, what is claimed as new is:

1. '111e process of manufacturing a sulphurized oil product from a cracked petroleum oil polymer which comprises passing the polymer oil to be sulphurized in intimate contact with gases containing hydrogen sulphide in a scrubbing zone, thereafter intimately mixing the polymer oil with hydrogen sulphide gas-` and oxygen, passing the resulting mixture in a stream through a heating zone and heating it to a temperature suiiicient to cause a reaction between the constituents of the stream and thereby sulphurize said polymer oil, conducting the resulting mixture of heated constituents into an enlarged reaction zone in which a body of the liquid polymer oil is maintained, passing the unreacted gases of said stream in intimate contact with said body of oil to complete the sulphurization reactionto the desired extent, and withdrawing the sulphurized polymer oil product from said reaction zone.

2. The processdened by claim 1 in which the polymer oil contains a substantial proportion of aromatic hydrocarbons.

3. 'I'he process defined by claim 1 in which the relative proportions of oxygen and hydrogen sulphide are regulated to provide sumcient oxygen to convert the hydrogen sulphide into nascent sulphur in the presence of the polymer oil which is intimately mixed therewith. V

4. The process of sulphurizing a hydrocarbon polymer oil, which comprises intimately mixing the polymer oil with a regulated proportion of hydrogen sulphide gas and a gas containing free oxygen, passing the resulting mixture in a coniined stream of restricted cross section through a heating zone in which the mixture is heated to a temperature of approximately 250 F. which is suillcient to cause the sulphurization oi the oil, controlling the ratio of hydrogen sulphide to oxygen containing gas so that suiicient oxygen is supplied to convert the sulphur in the hydrogen sulphide into an available form for sulphurizing the polymer oil, and separating the sulphurized polymer oil from the gaseous products of. reaction.

5. The process deiined by claim 4 in which said polymer oil comprises a substantial proportion of aromatic hydrocarbons.

6. The process dened by claim 4 in which said polymer oil comprises a substantial proportion of compounds containing a substituted benzene ring.

'1. The process of sulphurizing hydrocarbon compoundsl which comprises heating and intimately contacting the hydrocarbon compounds to be sulphurized -with hydrogen sulphide and an oxygen containing gas, regulating the relative proportions of hydrogen sulphide and oxygen to each other and to thehydrocarbon compounds, and separating the sulphurized hydrocarbon material from the resulting gaseous products of the reaction. I

, 8. 'Ihe process deflned by claim 7 in which said hydrocarbon compounds comprise side chained aromatic hydrocarbons.

9. The process dened by claim 7 in which said hydrocarbon compounds comprise a hydrocarbon polymer oil.

10. 'Ihe process dened by claim 'Iv in which said hydrocarbonV compounds are derived from cracked gasoline. v

11. A product of manufacture comprising essentially a sulphurized aromatic polymer oil containing from 20% to 30% of combined sulphur and having an amber color. A

12. A product of manufacture, comprising essentially a sulphurized hydrocarbon polymer oil containing a substantial proportion of compounds containing a benzene ring to which one or more side chains are attached. said product having a light color and being relatively free flowing at ordinary temperatures.

13. The process of sulphurizing hydrocarbon compounds. which comprises heating and intimately contacting the hydrocarbon compounds to be sulphurized with hydrogen sulphide in the presence of free oxygen in a proportion adapted to cause chemical combination of the sulphur contained in the hydrogen sulphide with the hydrocarbon compounds, and separating the sul phurized hydrocarbon material from the resulting gaseous reaction products.

WILLIAM E. FORNEY. 

